Fusion Engineering and Design 9899 (2015) 17551758

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Fusion Engineering and Design

journal homepage: www.elsevier.com/locate/fusengdes

Experimental study of permeation and selectivity of zeolite

membranes for tritium processes
Olga Borisevich, Rodrigo Antunes, David Demange
Karlsruhe Institute of Technology (KIT), Institute for Technical Physics, Tritium Laboratory Karlsruhe (TLK), Hermann von Helmholtz Platz 1,
76344 Eggenstein Leopoldshafen, Germany

h i g h l i g h t s

We report about new experimental results on advanced membranes for tritium processing especially for the DEMO breeding blanket.
High permeances are measured on different zeolite MFI membranes made by lm deposition or pore plugging.
Selectivity for H2 /He is limited requiring a multi-stage membrane process.
Selectivity of H2 O/He seems high enough to operate one single module.

a r t i c l e i n f o a b s t r a c t

Article history: Zeolites are known as tritium compatible inorganic materials widely used in packed beds as driers in
Received 2 October 2014 detritiation systems and are also suggested for tritium removal from helium at cryogenic temperature.
Received in revised form 26 March 2015 The Tritium Laboratory Karlsruhe (TLK) proposed a new fully continuous approach for tritium extraction
Accepted 6 April 2015
from the solid breeding blanket of fusion machines that improves the overall tritium management and
Available online 27 May 2015
minimizes both the tritium inventory and processing time. It is based on membrane permeation as a
pre-concentration stage upstream of a nal tritium recovery stage using a catalytic Pd-based membrane
Keywords:
reactor. Zeolite membranes were identied as the most promising candidates for the pre-concentration
Zeolite membrane
Breeding blanket
stage. In the present work the tubular zeolite MFI membrane provided by the Institute for Ceramic Tech-
Tritium extraction system nologies and Systems (IKTS, Hermsdorf, Germany) is studied to consolidate the proposed approach. The
permeation measurements for single gases hydrogen (replacing radioactive tritium) and helium, for
binary mixtures H2 /He and H2 O/He at different concentrations and temperatures are presented. The
tested membrane demonstrates a high performance, almost independent from the inlet composition in
the case of a gaseous mixture, while the transport in the presence of water vapour is strongly related to
the temperature of the mixture and component concentrations.
2015 Elsevier B.V. All rights reserved.

1. Introduction
Zeolites are inorganic porous materials widely known for their
adsorptive properties. Due to its tritium compatibility, zeolite
materials are proposed to be used in the Tritium Extraction Sys-
tem (TES) of the ITER Test Blanket Modules (TBM) for temperature
swing adsorption of Q2 (Q = H, D, T) [1] as well as for the removal
of tritiated water from the blanket purge gas in the adsorption col-
umn [2]. Recently the Tritium Laboratory Karlsruhe (TLK) proposed
a new concept for the TES for DEMO. This concept is based on the
use of zeolite membranes as a pre-concentration stage upstream
Corresponding author. Tel.: +49 721 608 22835.
E-mail address: david.demange@kit.edu (D. Demange).
of the catalytic membrane reactor PERMCAT [3] (Fig. 1). In this
approach both molecular and oxidized forms of tritium contained
in the purge gas are continuously processed, improving the overall
tritium management.
Over the last two decades, zeolite membranes have attracted the
interest of the scientic community. Indeed, many research groups
have reported results on newly developed membranes [4,5]. How-
ever, most of these membranes are produced at a lab scale, and only
few of them are commercially available. Additionally, the experi-
mental data for the extraction of Q2 or Q2 O from He with zeolite
membranes are rather scarce in the literature. Therefore, the TLK
started an experimental programme with the purpose of exploring
the potential of these membranes to be used in the TES for DEMO.
A composite MFI-alumina hollow bre membrane manufac-
tured by IRCELYON (France) was tested for single (He and H2 ),

http://dx.doi.org/10.1016/j.fusengdes.2015.04.015
0920-3796/ 2015 Elsevier B.V. All rights reserved.
1756 O. Borisevich et al. / Fusion Engineering and Design 9899 (2015) 17551758
Fig. 1. Advanced TES concept for the solid breeding blanket based on membrane
technology as an alternative to the conventional approach based on adsorption.
binary (H2 /He) and ternary (H2 /He/H2 O) gas mixtures [68]. The
results evidenced relatively high permeance but limited selectivity
for single gases. Similar separation performances were mea-
sured for H2 /He mixtures of different compositions. Additionally,
preferential permeability towards water in the ternary mixture
experiments was observed. In this paper, new experimental results
concerning the separation of H2 and H2 O from He obtained with a
new tubular MFI zeolite membrane are discussed and compared to
the previously reported data.
2. Zeolite membrane and experimental setup
2.1. Zeolite membrane
The tubular MFI membrane used in the present study was man-
ufactured by the Institute for Ceramic Technologies and Systems
(IKTS, Hermsdorf, Germany) (Fig. 2). The zeolite layer with pore
sizes of 0.51 nm 0.56 nm and a thickness of 3060 m is syn-
thesized on the inner surface of a TiO2 support (length = 250 mm;
inner/outer diameter = 7/10 mm). To perform the tests the mem-
brane was sealed inside a stainless steel module (Fig. 2) with two
EPDM O-rings. The module is equipped with connections for the
feed (injected stream), permeate (stream owing across the mem-
brane) and retentate (rejected stream) process gases. More details
can be found in Refs. [9,10].
Fig. 2. MFI tubular membrane (top) and the membrane module (bottom). The sweep
gas connection was not used.
Fig. 3. Schematic view of the ZIMT facility. The membrane module is represented
in shaded grey. (MFC mass ow controller, PR pressure regulator, PC pressure
controller, HS humidity sensor, MSB molecular sieve bed, QMS quadrupole
mass spectrometer).
2.2. Experimental setup and procedure
The membrane module was inserted into the dedicated facil-
ity ZIMT (Zeolite and Inorganic Membranes for Tritium), recently
built to measure the performances of zeolite membranes for single,
binary and ternary gas mixtures (Fig. 3). For this work, H2 and He
single gas experiments as well as H2 /He and H2 O/He binary mixture
experiments have been performed.
In single gas tests a constant ow of H2 or He is injected into the
module in the dead-end mode (retentate closed), and the pressure
difference across the membrane is then measured by two pressure
sensors (MKS 750 B).
The permeance of the gas i is determined by
Pi
i = (1)
A(pf pp )
where Pi is the permeate ow (mol/s), A is the membrane sur-
face area (m2 ), pf and pp are the feed and permeate pressures (Pa),
respectively.
The ideal selectivity of the membrane is dened as the ratio of
the single gas permeances of the gases i and j:
i
i/j = (2)
j
In the H2 /He binary experiments, different gas mixture com-
positions were obtained using mass ow controllers (MKS
Instruments, type MF1). In this mode the retentate was opened
and the ows were regulated for cut adjustment (ratio of perme-
ate to the feed ow). The composition of the process streams was
analysed by a mass-spectrometer (QMG 220, Pfeiffer-Vacuum).
For the measurements with water vapour an evaporation sys-
tem comprised by a liquid ow controller (LIQUI-FLOW L13,
Bronkhorst High Tech) and a vaporizer (aSTEAM DV2, Adrop) were
used. The moisture of the process streams was measured by two
humidity sensors (Michell Instruments).
The concentrations measured in the binary mode are used for
determining the separation factor given by
yi /yj
i/j = , (3)
xi /xj
where x and y are the component concentrations in the feed and
permeate, respectively. The experimental conditions are summa-
rized in Table 1.
3. Results and discussions
3.1. Single gas experiment
The single gas permeances of H2 and He for the tubular MFI
membrane (IKTS) as well as the ideal selectivity as a function of
temperature are presented and compared with the previous results
(IRCELYON) in Fig. 4. The temperature range is limited to 130 C
for the IKTS membrane by the thermal resistance of the EPDM-
type sealing. The permeance of both gases is considerably higher
 O. Borisevich et al. / Fusion Engineering and Design 9899 (2015) 17551758 1757

Table 1 0.1% 1% 10% 1% IRCELYON

Experimental conditions of the single and binary tests with the MFI membrane (F
2.0
inlet ow, pf feed pressure, pp permeate pressure, T temperature of the
module).

Mode F (ml/min) pf (hPa) pp (hPa) T ( C)

1.8

Separation factor
Single gas Up to 700a 15002500 1000 22130
H2 /He 1250 10004000 300 22 1.6
650 10004500 300 77; 100
H2 O/He
1150 10004500 300 30100
1.4
a
Measured for hydrogen.

1.2

for the hollow ber (IRCELYON) than for the tubular one (IKTS),
1.27 and 0.78 mol/m2 s Pa, respectively for hydrogen at room
temperature (RT). This result reects the difference in the zeolite
thickness of the membranes (1 m for IRCELYON and 3060 m
for IKTS) due to the synthesis methods (secondary growth for the
IKTS case and pore-plugging for the IRCELYON). Nevertheless the
ideal H2 /He selectivities measured for both membranes are consis-
tent, not exceeding 2.2 at RT. A further increase of the temperature
leads to the decrease of the selectivity reaching the Knudsen selec-
tivity of 1.4. The higher permeances for H2 are due to its stronger
adsorption in the zeolite pores [11]. In addition, the tempera-
ture dependency of the permeation of both gases is in agreement
with the well-known StefanMaxwell transport mechanism of light
gases in zeolite membranes [11,12].
H2 IKTS H2 IRCELYON He IKTS He IRCELYON
1.6
Permeance (mol/m2sPa)
1.0
0.0 0.2 0.4 0.6 0.8
cut
Fig. 5. Separation factor H2 /He of the tubular MFI membrane as a function of cut, at
RT.
3.2. Mixture H2 /He
The separation factor of the binary mixture H2 /He was mea-
sured at RT as function of cut at three hydrogen concentrations:
0.1%, 1%, 10% (Fig. 5). This dependency has a maximum at a cut 0.3,
which corresponds to the optimal process parameter. This obser-
vation is also conrmed by a numerical simulation performed at
TLK [6].
The molecular-sieve mechanism to separate the gas mixture is
expected to have no relevance since the kinetic diameters of the
involved molecules (0.26 nm for He and 0.289 nm for H2 ) are well
below the pore sizes of the crystalline structure of the material. In
fact, the obtained separation factor is slightly lower than the ideal

selectivity. These observations can be explained by two reasons.

First, H2 is preferentially adsorbed in the zeolite pores hindering the
1.2 permeation of He. Secondly, the gradual depletion of the hydrogen
in the feed leads to the decreasing of the process driving force along
the membrane. A simulation tool is being developed at the TLK to
0.8 better understand this mutual interaction.
Moreover, the separation factor is observed to be almost
independent from the mixture composition in the range of the
0.4 experimental error (10%) being well in agreement with the results
for the MFI hollow bre.

0.0
0 100 200 300 400 500 3.3. Mixture H2 O/He
T ( C)
The binary mixture H2 O/He was rst tested with 6% and 1% of
IRCELYON IKTS
water vapour at two temperatures: 100 and 77 C. The separation
factor of the mixture with 6% of water vapour is 1.9 and 1.1 at 77
2.5 and 100 C, respectively. For the 1% case, these values increase to
3.7 and 1.8.
On the one hand, the dependency of the separation factor on
the concentration is not well understood by the authors, and more
Ideal selectivity

2.0 comprehensive and systematic experiments are being performed

to improve our understanding.
On the other hand, the increase of the separation factor with
the decrease of the temperature is due to the stronger adsorption
1.5
of H2 O in the zeolitic pores hindering the permeation of He. This is
demonstrated in a second experiment, where the mixture with 1%
of water was tested in the temperature range 30100 C (Fig. 6). At
1.0 30 C the separation factor increases up to 6. Due to the adsorp-
0 100 200 300 400 500 tion of water in the membrane, the experimental regulation of the
cut was difcult. The obtained separation factors are signicantly
T ( C)
lower than the expected ones from the previous experiments on
Fig. 4. Single permeance of H2 and He (top) and ideal selectivity H2 /He (bottom) as the hollow bre with the ternary mixture H2 O/H2 /He of composi-
a function of temperature for two different MFI membranes. tion 1%/1%/99% [8]. The pre-saturation of the membrane by water
1758 O. Borisevich et al. / Fusion Engineering and Design 9899 (2015) 17551758
7 The ongoing experimental campaign at the TLK includes the
H 2O/He Separation Factor
5 tested with tritium.
3 pre-concentration of the TES.
1 The authors thank IRCELYON France (M. Pera Titus) and IKTS
0 20 40 60 80
T ( C)
Fig. 6. The separation factor of the binary mixture H2 O/He as a function of temper-
ature.
vapour or the increase of the driving force to intensify the separa-
tion process was concluded as a possible solution of the problem
after discussion with the membrane provider.
Nevertheless, the measured separation factors suggest that
doping the purge gas of the breeding blanket with H2 O (instead of
H2 , as presently considered [13]) can signicantly reduce the size
of the membrane cascade for the pre-concentration step considered
in the simulation results previously reported [8].
4. Conclusion
Gas separation experiments in zeolite membranes for the TES
of the breeding blanket are being performed at the TLK. A newly
developed tubular MFI membrane was tested for single (H2 and He)
and binary mixtures (H2 /He and H2 O/He) at different temperatures
and concentrations. The highest H2 /He ideal selectivity (2.2) was
obtained at RT. By diluting H2 in He, a maximum separation factor of
1.7 (at a cut 0.3) was obtained at the same temperature regardless
of the feed composition. Higher separation factors were obtained
for the mixture 1%/99% H2 O/He with a value of 6 at RT. These
results are in general agreement with the results reported for a
previously tested MFI hollow bre membrane.
Due to the superior permeability of water vapour for the MFI
material, the use of H2 O instead of H2 as the dopant for the purge
gas shall be considered. In this case, not only a higher efciency
of the extraction of vapour from helium by zeolite membranes is
ensured, but also the vapour reduces the tritium losses by per-
meation through the structure materials into the coolant. Such
alternative approaches have to be balanced and could be studied at
rst with ITER-TBMs.
study of a NaA-type zeolite membrane as well as a carbon mem-
brane. In addition, more comprehensive studies will be performed
on MFI membranes to identify the most promising one to be later
The experimental results are meant to be implemented into a
numerical simulation tool under development at the TLK for a thor-
ough analysis of their inuence on the design considerations for the
Acknowledgments
100 120 Hermsdorf Germany (H. Richter) for providing the membrane spec-
imens and for the fruitful discussions. This project has received
funding from the European Unions Horizon 2020 Research and
Innovation Programme under grant agreement number 633053.
The views and opinions expressed herein do not necessarily reect
those of the European Commission.
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